CN105709574A - Efficient stokerfeed boiler ozonation desulfurization and denitrification integrated process system - Google Patents
Efficient stokerfeed boiler ozonation desulfurization and denitrification integrated process system Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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Abstract
The invention relates to an efficient stokerfeed boiler ozonation desulfurization and denitrification integrated process system. The system mainly comprises a flue gas system, an air source oxygen generation system, an oxygen storage and supply system, an ozone generation system, a recirculating cooling water system, an ozone injection system, an absorption tower system, a process water system, a compressed air system, a magnesium oxide method flue gas desulphurization system, a gas flow measuring system, a high-low pressure distribution and control system and the like. According to the efficient stokerfeed boiler ozonation desulfurization and denitrification integrated process system, the ozonation oxidation technology is utilized for flue gas denitrification, the strong oxidizing property of ozone is utilized for oxidizing a water-insoluble nitric oxide in flue gas into freely-soluble N2O5 and other gas and absorption is performed through a follow-up absorbing device. The technology has the advantage of being high in flue gas adaptability and can remove flue gas containing high dust content, the denitrification efficiency can reach 95%, and meanwhile the denitrification efficiency can be adjusted according to on-site requirements.
Description
Technical field
The present invention relates to a kind of efficiently chain furnace ozone oxidation desulfurization and denitrification integral process system, can be applicable to the flue gas managing technique of nitrogen-containing oxide and oxysulfide, carry out NOxAnd SOxEffective integrated combine elimination.
Background technology
Boiler combustion coal dust can to a large amount of pollutant of environmental emission, air NO according to statistics while carrying out energy conversionxIn discharge 67% comes spontaneous combustion coal, nitrogen oxides (NOx) discharge be the one of the main reasons causing a series of severe contamination problem such as acid rain, photochemical fog, therefore coal-fired boiler in power plant is carried out NOxControl processes and is highly desirable to.
The NO of more than 95% in boiler smokexWater insoluble for NO, NO, and the NO of high-valence state2、NO3、N2O5Generation HNO is reacted with water3, its solvability is greatly improved, thereby through changing NOxIt is feasible in theory that form realizes denitration.Argonne National Laboratory of the U.S. utilizes chloric acid and sodium chlorate that NO is converted to NO2Form, HgO are converted into the Hg of solubility2+, then pass through alkali liquor and absorb, it is possible to remove NO, SO simultaneously2, Hg, but chloric acid and chlorate corrosion are strong, non-degradable, it is easy to cause waste liquid secondary pollution.ECO (electro-catalyticoxidation) technology of POWERSPAN company exploitation, by plasma discharge, high-octane impulse electric corona produces OH, O, O3Deng free radical the efficient oxidation Elemental Mercury, NO, in conjunction with alkali liquor absorption and wet-esp simultaneously to SO2、NOx, Hg, PM, HCl control effectively.Ozone, as a kind of strong oxidizer, has been widely used in medicine and water process aspect, has carried out efficient sterilizing deodorization degradation of organic substances.Ozonator is for local air or oxygen discharge, and electric discharge is uniformly, power consumption is low, efficiency is high.Cannon has carried out part research with BOC Co. for ozone oxidation process, and result shows the NO of more than 90% to be oxidized to higher nitrogen oxides and absorbed by ozone oxidation.
Domestic, the study mechanism of Zhejiang University's heat energy institute application ozone simultaneous SO_2 and NO removal always for a long time, wherein professor's Wang Zhihua research shows NOxOxidation carry out step by step, first NO oxidation generate NO2, work as O3NO is generated after excessive3With a small amount of N2O5, at n (O3): < when 1, primary product is NO to n (NO)2、NO3, N2O5Only at O3Just producing under excess conditions, the result of the test carried out in multilamellar plug flow reactor and analog result are coincide good, demonstrate the correctness of this reaction mechanism further.Research finds that variations in temperature is for O under 100 DEG C and 200 DEG C of conditions simultaneously3And the oxidation reaction impact between NO is only small, as n (O3): during n (NO)=1.0, respectively reach the oxidation efficiency of 89.2% and 85.0%.The research and utilization ozone of doctor Jiang Shudong and bioactive molecule realize the relevant issues of multiple pollutant cooperation-removal and have carried out experiment and study mechanism, and main research includes solubility NOxWet method elimination, flue gas entirety catalytic oxidation pollutant are studied and are contrasted with ozone oxidation, the quantum Chemical Study of some unknown speed and the reaction of not bright mechanism, heterocatalysis oxygen produces bioactive molecule oxidation NO research, it was therefore concluded that: adopt ozone spraying technique elimination NOx, at O3When/NO mol ratio is more than 1, because gas phase generates NO3、N2O5, NOxElimination steeply rises, it is possible to reach more than 90%, simultaneously liquid phase NO3 -Concentration rises.
Ozone oxidation absorption process is denitration technology that is fast-developing in recent years and that rise, and basic fundamental route is: NOxMainly existing with the form of NO (accounting for more than 95%), the performance of NO characteristic is difficult is dissolved in water, causes it to be difficult to be converted absorption.NO can be oxidized to readily soluble N by the strong oxidizing property utilizing ozone2O5Deng gas, absorb again through follow-up absorption plant.
Ozone oxidation absorption process technical process is broadly divided into two steps: the oxidation of nitrogen oxides and the absorption of oxidation product.The oxidation of nitrogen oxides mainly carries out in flue, quickly nitrogen oxides in effluent is oxidized to N by the ozone sprayed into2O5；The absorption of oxidation product carries out in absorption tower, typically via the original desulfurizing tower of equipment, can be completed the absorbing and removing of nitrogen oxides by the basic anhydride sprayed into, generate nitrate.
Oxidizing and denitrating ozone technical characteristics is in that flue gas characteristic strong adaptability, can remove for high ash-laden gas；Denitration efficiency reaches as high as 95%, can adjust denitration efficiency according to requirements of the owner.
As seen from the above analysis, efficient chain furnace ozone oxidation desulfurization and denitrification integral process system is to have very much the new technique of development and application potentiality, has a good application prospect.Under the situation that environmental requirement improves day by day, the development of this process system and application have good economic and social benefit.
Summary of the invention
Present invention solves the technical problem that and be: design and have developed new and effective chain furnace ozone oxidation desulfurization and denitrification integral process system, by controlling ozone and magnesian straying quatity and spraying into position, ozone and magnesian straying quatity spray into according to needed for removing the pollutant contained in flue gas completely 0.6～1.5 times of equivalent.Spray into position: between furnace outlet to desulfurizing tower entrance, under the premise of the most short residence time needed for satisfied reaction, select optimum temperature window to spray into.Carry out flue gas pollutant and combine elimination, finally realize the qualified discharge of flue gas, reach the purpose of energy-saving and emission-reduction.
The technical solution of the present invention is:
A kind of efficiently chain furnace ozone oxidation desulfurization and denitrification integral process system, it is characterized in that, including one for preparing the air source oxygen generation system of oxygen, one passes through the oxygen surge tank that pipeline is connected with described air source oxygen generation system, and the oxygen in described oxygen surge tank is converted to the ozone generation system of ozone by one；Ozone is passed into and is used for absorbing NOx in absorption tower system by described ozone generation system.
In a preferred embodiment of the invention, also include ozone spraying system, be arranged between described ozone generation system and absorption tower system, for described ozone is injected in boiler suitable position flue.
In a preferred embodiment of the invention, described ozone generation system is connected to recirculating cooling water system by pipeline, this recirculating cooling water system for the cooling of ozone generation system to ensure that the temperature of ozone generation system is lower than 30 DEG C.
In a preferred embodiment of the invention, described air source oxygen generation system includes aerator, the air filter being connected with aerator, raw air removes mechanical admixture in air through air filter, after aerator compresses, entering adsorber from adsorber bottom charging aperture, the component such as nitrogen in air, carbon dioxide is adsorbed, and oxygen product flows out from adsorber top.
In a preferred embodiment of the invention, described ozone generation system includes ozonator, power supply of ozonizer system and control system, it is provided with ozonator cell in described ozonator, wherein in ozonator cell partial oxidation by medium-frequency high-voltage electric discharge become ozone, ozone through temperature, pressure, flow monitoring regulate after by ozone outlet output.
In a preferred embodiment of the invention, the admission line of described ozonator devises relief valve, open after system pressure exceedes design load, to ensure system operational security；Described ozonator cell is additionally provided with ozone taking QI KOU, the concentration of giving vent to anger of the ozone concentration detector on-line monitoring ozonator by being equipped with at ozonator.
In a preferred embodiment of the invention, described recirculating cooling water system comprises circulating cooling tower, cold remove circulating pump, the supporting plate type heat exchanger of ozonator, ozonator internal heat parts, the supporting plate type heat exchanger of described ozonator, ozonator internal heat parts and associated conduit constitute closed circulation system, and its medium is slagging-off, deoxygenation after-tack pure water；Circulating cooling tower, coolant circulation pump, the supporting plate type heat exchanger of ozonator collectively constitutes open type external circulating system, is used for cooling down closed circulation system recirculated water.
In a preferred embodiment of the invention, described ozone spraying system includes ozone flow distributing system, and device and injecting-unit are monitored in flow-control, and described injecting-unit outlet pressure is about 0.095MPa.
In a preferred embodiment of the invention, also it is injected with magnesium oxide, described ozone and magnesian straying quatity in described absorption tower system to spray into according to needed for removing the pollutant contained in flue gas completely 0.6～1.5 times of equivalent.
The present invention compared with prior art provides the benefit that:
(1) the Ozonation denitrating technique system of the present invention, the optimal reaction temperature interval of this system is < 250 DEG C, limit without low temperature, for 850 DEG C of temperatures above demands of SNCR technique and 300～400 DEG C of temperature windows of SCR technique, applied widely.
(2) Ozonation denitration technology denitration efficiency is high, and can adjust denitration efficiency, wide accommodation according to demand.This technological transformation workload is little, only suitable with SNCR, compares and SCR technique, without boiler flue is carried out bigger change, without influence on stable operation of the boiler, short construction period, without liquefied ammonia and ammonia equipment, required raw material is only air and water, will not surrounding be impacted.
(3) this integration combined desulfurization and denitration system flow resistance is little, and mixing efficiency is high.SR is well below SCR system resistance, and the low flow resistance of system is not only able to ensure that ozone sprays into flue smoothly, simultaneously capable of reducing energy consumption；High efficient mixed, it is ensured that ozone well mixes with flue gas, fully reacts, and has significantly high ozone utilization rate while improving denitration efficiency.
(4) magnesium oxide method sulfur removal technology is adopted, while satisfied relatively high desulfurization efficiency, to product Mg2SO4Recycling, it is achieved recycling economy, whole sulfur removal technology no waste discharge, secondary pollution will not be produced.
(5) in this integration desulfurization denitration cooperation-removal system, Ozonation denitrating technique and magnesium oxide method sulfur removal technology share an absorption tower, the integrative coordinated elimination of desulphurization denitration single column can be carried out in this absorption tower simultaneously, need not additionally build tower, therefore there is the advantage that cost of investment is low, removal efficiency is high..
Accompanying drawing explanation
Fig. 1 is the system process figure of the present invention.
Detailed description of the invention
Below in conjunction with flow sheet, the present invention is described in further detail:
With reference to Fig. 1, a kind of efficiently chain furnace ozone oxidation desulfurization and denitrification integral process system, it is characterized in that, including one for preparing the air source oxygen generation system of oxygen, one passes through the oxygen surge tank that pipeline is connected with described air source oxygen generation system, and the oxygen in described oxygen surge tank is converted to the ozone generation system of ozone by one；Ozone is passed into and is used for absorbing NOx in absorption tower system by described ozone generation system, also includes ozone spraying system in this system, is arranged between described ozone generation system and absorption tower system, for being injected in boiler suitable position flue by described ozone.
Additionally described ozone generation system is connected to recirculating cooling water system by pipeline, this recirculating cooling water system for the cooling of ozone generation system to ensure that the temperature of ozone generation system is lower than 30 DEG C.
It is described in further detail below for each system above-mentioned:
1, air source oxygen generation system
This patent adopts air source oxygen generation system, adopts gauge pressure absorption method (VPSA) oxygen producing.The oxygen concentration and flow produced can be regulated according to the actual requirements.
VPSA oxygenerator adopts two tower pressure-variable adsorption vacuum desorption technological processes.Complete set of equipments is regulated by aerator, vacuum pump, adsorber, instrument air system, blind controller system, electric control system, switched system, oxygen compressor, pressure oxygen, is sent 10 parts such as oxygen adjustment and system to form.Raw air removes mechanical admixture in air through air filter, and after aerator compresses, (built-in being filled with of adsorber has selective absorption water in air gas, CO to enter adsorber from adsorber bottom charging aperture2With the adsorbent of Hydrocarbon, be also equipped with the oxygen molecular sieve with nitrogen in selective absorption air), the component such as nitrogen in air, carbon dioxide is adsorbed, and oxygen product flows out from adsorber top.After molecular sieve adsorption is saturated, makes absorbed component desorbing by reducing adsorber operating pressure and flow out adsorber.Each circulation, adsorber all experienced by absorption, forward bleeds off pressure, vacuum desorption, all pressure, five job steps of pressurising.The conversion of each job step of adsorber is that the switching by operated pneumatic valve realizes.The action of pneumatic switching valve, is regularly automatically switched according to the programme-control set by PLC control system.
2, oxygen storage supply system
Oxygen storage supply system act as storage ozonator and prepares the oxygen needed for ozone, and is supplied to ozonator as required, and this system possesses remote control function, it is possible to according to process system demand, automatically controls supply amount of oxygen.This system comprises equipment: oxygen storage tank is a set of, carburator two, and related valve and control valve group are a set of, and equipment Foundations are a set of.
3, ozone generation system
Ozone generation system comprises the ozone generation system of complete set.Ozone generation system is made up of the attached device etc. in ozonator, power supply of ozonizer system, control system and complete set of equipments, and native system possesses the ability producing process system ozone consumption 110% ozone.
According to the principle of system equipment economical operation, ozonator selects specified ozone concentration 148mg/L (or 148g/Nm3, being equivalent to quality-mass concentration is 10wt%).Ozonator can realize yield smooth adjustment, and adopts the mode simultaneously adjusting power and tolerance to realize the requirement of variable concentrations and yield.Ozonator adopts closed-circuit cooling water system, can effectively prevent because of the outer circulation change of water quality (especially chloride ion and the pH value) corrosion to ozonator.Ozonation system adopts automatic control mode and good man machine interface, decreases operation easier, simultaneously by online monitoring system to operational factor monitor in real time, provides safeguard for ozonation system is properly functioning.
The admission line of ozonator devises relief valve, opens after system pressure exceedes design load, to ensure system operational security.In ozonator cell partial oxidation by medium-frequency high-voltage electric discharge become ozone, product gas through temperature, pressure, flow monitoring regulate after by ozone outlet output.Ozonator cell is provided with ozone taking QI KOU, the concentration of giving vent to anger of the ozone concentration detector on-line monitoring ozonator by being equipped with at ozonator.
Ozonation system adopts automatic control mode and good man machine interface, decreases operation easier, simultaneously by online monitoring system to operational factor monitor in real time, provides safeguard for ozonation system is properly functioning.
4, recirculating cooling water system
Recirculating cooling water system effect is the cooling providing necessity for ozonator; owing to when temperature raises, ozone can be decomposed; ozonator need to ensure that (ozonator internal device temperature raises the recirculated cooling water lower than 30 DEG C to cool down this equipment; ozone generator efficiency can reduce) cooling water temperature more than 38 DEG C time, ozonator report to the police shut down.
This process cycles cooling water system comprises circulating cooling tower, coolant circulation pump, the supporting plate type heat exchanger of ozonator, ozonator internal heat parts, associated conduit valve instrument etc..Wherein, the supporting plate type heat exchanger of ozonator, ozonator internal heat parts and associated conduit constitute closed circulation system, and its medium is slagging-off, deoxygenation after-tack pure water；Circulating cooling tower, the cold circulating pump that goes, the supporting plate type heat exchanger of ozonator collectively constitutes open type external circulating system, is used for cooling down closed circulation system recirculated water.
5, ozone spraying system
Ozone spraying system act as to be spurted in boiler suitable position flue by the ozone being delivered to boiler area by insulation ozone pipeline, spraying system requires: low flow resistance, ozone is about 0.095MPa from generator outlet pressure, owing to himself there is strong oxidizing property and easily decomposing, Gu Chouyangfashengqikou is without pressurization measure, and the low flow resistance of spraying system can ensure that ozone sprays into flue smoothly；High efficient mixed, it is ensured that ozone well mixes with flue gas, fully reacts.
Ozone spraying system includes ozone flow distributing system, flow-control monitoring device, injecting-unit gas nozzle etc., wherein ozone house steward to comprise flow distributing system a set of.
6, absorption tower system
Described magnesium oxide method absorption tower system is made up of magnesium oxide storage tank, desulfurizing tower, the main device of spray and correlate meter pipeline.Ozonation denitration and magnesium oxide method desulfurization can be carried out in this absorption tower simultaneously, the integrative coordinated elimination of desulphurization denitration single column can be accomplished, it is not necessary to additionally build tower, therefore there is the advantage that cost of investment is low, removal efficiency is high.
Ozone oxidation absorb the big feature of denitrating technique one for may utilize the original desulphurization absorption tower system of boiler, need not newly-built absorption tower, can accomplish that desulfurization and denitrification integral absorbs.Therefore, this programme implementation process can share an absorption tower with desulphurization system, select suitable position to spray into appropriate ozone before the absorption tower in magnesium oxide method desulphurization system, the efficient removal of nitrogen oxides can be reached.
Combined desulfurization and denitration is carried out in conjunction with magnesium oxide method by Ozonation.Air enters oxygen generation system after being pressurizeed by roots blower, obtains the oxygen of purity 90%, the O that oxygenerator prepares subsequently2Entering oxygen storage supply system to keep in, supply system is by oxygen supply to ozonator according to actual needs, and supply system possesses remote control function, it is possible to automatically control supply oxygen flow according to process system actual demand.
Oxygen obtains the ozone of certain purity and pressure after entering ozonator.Ozonator can realize yield smooth adjustment, and adopts the mode simultaneously adjusting power and tolerance to realize the requirement of variable concentrations and yield.Ozonator can produce heat at work, and in order to ensure that equipment operating temperature is not more than 30 DEG C, arranging recirculating cooling water system is that ozone generation system is lowered the temperature.Ozone sprays into flue before desulfurizing tower through jet module, with NO in flue gas in fluexThere is oxidation reaction, the main component N of generation2O5Enter desulfurizing tower reaction with flue gas, and ultimately generate nitrate.
The foregoing description of present embodiment and accompanying drawing represent the preferred version of the present invention, being embodied as can according to actual boiler type and tail flue gas parameter not necessarily departing from the adjustment and optimization that carry out concrete technology parameter in the scope that the claims in the present invention define, therefore, the present invention is widely.
Claims (9)
1. an efficient chain furnace ozone oxidation desulfurization and denitrification integral process system, it is characterized in that, including one for preparing the air source oxygen generation system of oxygen, one passes through the oxygen surge tank that pipeline is connected with described air source oxygen generation system, and the oxygen in described oxygen surge tank is converted to the ozone generation system of ozone by one；Ozone is passed into and is used for absorbing NOx in absorption tower system by described ozone generation system.
2. one according to claim 1 efficient chain furnace ozone oxidation desulfurization and denitrification integral process system, it is characterized in that: also include ozone spraying system, it is arranged between described ozone generation system and absorption tower system, for described ozone is injected in boiler suitable position flue.
3. one according to claim 1 efficient chain furnace ozone oxidation desulfurization and denitrification integral process system, it is characterized in that: described ozone generation system is connected to recirculating cooling water system by pipeline, this recirculating cooling water system for the cooling of ozone generation system to ensure that the temperature of ozone generation system is lower than 30 DEG C.
4. one according to claim 1 efficient chain furnace ozone oxidation desulfurization and denitrification integral process system, it is characterized in that: described air source oxygen generation system includes aerator, the air filter being connected with aerator, raw air removes mechanical admixture in air through air filter, after aerator compresses, entering adsorber from adsorber bottom charging aperture, the component such as nitrogen in air, carbon dioxide is adsorbed, and oxygen product flows out from adsorber top.
5. new and effective chain furnace ozone oxidation desulfurization and denitrification integral process system according to claim 1, it is characterized in that: described ozone generation system includes ozonator, power supply of ozonizer system and control system, it is provided with ozonator cell in described ozonator, wherein in ozonator cell partial oxidation by medium-frequency high-voltage electric discharge become ozone, ozone through temperature, pressure, flow monitoring regulate after by ozone outlet output.
6. new and effective chain furnace ozone oxidation desulfurization and denitrification integral process system according to claim 1 or 5, it is characterized in that: the admission line of described ozonator devises relief valve, open after system pressure exceedes design load, to ensure system operational security；Described ozonator cell is additionally provided with ozone taking QI KOU, the concentration of giving vent to anger of the ozone concentration detector on-line monitoring ozonator by being equipped with at ozonator.
7. new and effective chain furnace ozone oxidation desulfurization and denitrification integral process system according to claim 3, it is characterized in that: described recirculating cooling water system comprises circulating cooling tower, cold remove circulating pump, the supporting plate type heat exchanger of ozonator, ozonator internal heat parts, the supporting plate type heat exchanger of described ozonator, ozonator internal heat parts and associated conduit constitute closed circulation system, and its medium is slagging-off, deoxygenation after-tack pure water；Circulating cooling tower, coolant circulation pump, the supporting plate type heat exchanger of ozonator collectively constitutes open type external circulating system, is used for cooling down closed circulation system recirculated water.
8. new and effective chain furnace ozone oxidation desulfurization and denitrification integral process system according to claim 2, it is characterized in that: described ozone spraying system includes ozone flow distributing system, flow-control monitoring device and injecting-unit, described injecting-unit outlet pressure is about 0.095MPa.
9. the new and effective chain furnace ozone oxidation desulfurization and denitrification integral process system according to any claim of claim 1-5, it is characterized in that: be also injected with magnesium oxide, described ozone and magnesian straying quatity in described absorption tower system and spray into according to needed for removing the pollutant contained in flue gas completely 0.6～1.5 times of equivalent.
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| CN109603463A (en) * | 2018-12-28 | 2019-04-12 | 中国空气动力研究与发展中心超高速空气动力研究所 | A kind of absorption plant and absorption process of arc tunnel high concentration huge discharge nitrogen oxides tail gas |
| CN109698256A (en) * | 2018-12-29 | 2019-04-30 | 无锡琨圣科技有限公司 | A kind of silicon chip surface oxidative system and method |
| CN110394044A (en) * | 2019-08-04 | 2019-11-01 | 广州格邦机械工程有限公司 | Low-temperature flue gas ozone denitrating system |
| CN111514694A (en) * | 2020-04-29 | 2020-08-11 | 中国建材国际工程集团有限公司 | Glass flue gas recovery method |
| CN111603913A (en) * | 2020-06-09 | 2020-09-01 | 周昊 | System and method for treating liquid slag discharging boiler waste gas of ozone denitration coal-fired power plant |
| CN112604476A (en) * | 2020-12-29 | 2021-04-06 | 浙江百能科技有限公司 | Method for recycling oxygen in boiler flue gas ozone oxidation denitration process |
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